Effect of polymerization on free water in polyacrylamide hydrogels observed with Brillouin spectroscopy.

Brillouin spectroscopy is used to determine the effects of polymer concentration, crosslinking density, and polymerization on the longitudinal storage and loss moduli of polyacrylamide hydrogels. The model established by Chiarelli et al. is implemented to calculate the speed of sound in the free water [Chiarelli et al., The Journal of the Acoustical Society of America, 2010, 127(3), 1197-1207]. The polymer concentration has the greatest effect on the moduli of the polymer matrix. We determined that the crosslink density has no measurable effect on the logitudinal storage or loss modulus of polyacrylamide hydrogels when measurements are made at GHz frequencies, in contrast to measurements made at kHz frequencies as documented by other studies. However, the moduli are independent of monomer concentration if the acrylamide is not polymerized. We show at the GHz frequency that the incorporation of acrylamide polymer chains affects the mechanical properties of the free water. The speed of sound in the free water is reduced by the introduction of polymerized acrylamide. The long polymer chains and their interactions with the bounded water disrupt the bonding organization of the unbound water, causing a reduction of the average hydrogen bond strength between free water molecules. This results in a decreased speed of sound in the free water and an increase in the longitudinal storage modulus of the hydrogel.

Vibrational spectroscopy investigation of defects in Zr- and Hf-UiO-66.

Defect engineering in metal-organic framework compounds has allowed for improvements in catalysis-based functionalities, gas sensing, and gas storage. Metal-organic framework UiO-66 compounds with Zr- and Hf-based metal secondary building units were studied with Raman and infrared vibrational spectroscopy. Missing linker and missing cluster defects were engineered into the crystal structure via a modulated synthesis technique. Missing cluster defects in Hf-UiO-66 are first characterized by powder X-ray diffraction (PXRD) whereby two low-angle peaks were fit to extract the relative quantity of reo topology in four defective samples. A monotonic red-shift of the Raman-active Hf-O coordination bond vibration is interpreted as a signature of missing cluster defects, resulting from less-rigid charge-balancing monocarboxylate formate ions replacing the dicarboxylate linker molecule. This signature is hypothesized to be independent of the topology in which the defects appear. Missing linker defects in Zr-UiO-66 are characterized by infrared absorption spectroscopy by the quenching of C-C and C-H vibrational modes confined to the linker molecule. Together, Raman and infrared vibrational spectroscopies coupled with standard characterization techniques are employed to directly probe the nature of defects as well as offer new characterization tools for missing cluster defects in UiO-66.

Electron-phonon coupling in anthracene-pyromellitic dianhydride.

In this study, the electron-phonon coupling constants of the mixed-stack organic semiconductor anthracene-pyromellitic dianhydride (A-PMDA) are determined from experimental resonant Raman and absorption spectra of the charge transfer (CT) exciton using a time-dependent resonant Raman model. The reorganization energies of both intermolecular and intramolecular phonons are determined and compared with theoretical estimates derived from density functional theory calculations; they are found to agree well. We found that the dominant contribution to the total reorganization energy is due to intramolecular phonons, with intermolecular phonons only contributing a small percentage. This work goes beyond prior studies of the electron-phonon coupling in A-PMDA by including the coupling of all Raman-active phonons to the charge transfer exciton. The possibility of orientational disorder in A-PMDA at 80 K is inferred from the inhomogeneous broadening of the absorption line shape.

Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study.

We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoretical Raman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.

Freezing-in orientational disorder induces crossover from thermally-activated to temperature-independent transport in organic semiconductors.

The crystalline structure of organic materials dictates their physical properties, but while significant research effort is geared towards understanding structure-property relationships in such materials, the details remain unclear. Many organic crystals exhibit transitions in their electrical properties as a function of temperature. One example is the 1:1 charge-transfer complex trans--stilbene-2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. Here we show that the mobility and resistivity of this material undergo a transition from being thermally activated at temperatures above 235 K to being temperature independent at low temperatures. On the basis of our experimental and theoretical results, we attribute this behaviour to the presence of a glass-like transition and the accompanied freezing-in of orientational disorder of the stilbene molecule.

Atomically flat, large-sized, two-dimensional organic nanocrystals.

Large-sized, 2D single crystals of perylene are grown by both solution-cast and physical vapor transport methods. The crystals have a atomically flat parallelogram morphology and the aspect ratios of the lateral extension compared to the thickness are up to 10(3) . The atomically flat feature leads to good interface contact, making a single-crystal field-effect transistor with higher mobility. The mobility of atomically flat crystals can be 10(3) -10(4) times higher than rough crystals.

Nanoforest Nb2O5 photoanodes for dye-sensitized solar cells by pulsed laser deposition.

Vertically aligned bundles of Nb(2)O(5) nanocrystals were fabricated by pulsed laser deposition (PLD) and tested as a photoanode material in dye-sensitized solar cells (DSSC). They were characterized using scanning and transmission electron microscopies, optical absorption spectroscopy (UV-vis), and incident-photon-to-current efficiency (IPCE) experiments. The background gas composition and the thickness of the films were varied to determine the influence of those parameters in the photoanode behavior. An optimal background pressure of oxygen during deposition was found to produce a photoanode structure that both achieves high dye loading and enhanced photoelectrochemical performance. For optimal structures, IPCE values up to 40% and APCE values around 90% were obtained with the N(3) dye and I(3)(-)/I(-) couple in acetonitrile with open circuit voltage of 0.71 V and 2.41% power conversion efficiency.

Influence of vibronic coupling on band structure and exciton self-trapping in α-perylene.

Exciton sizes influence transport processes and spectroscopic phenomena in molecular aggregates and crystals. Thermally driven nuclear motion generally localizes electronic states in equilibrium systems. Exciton sizes also undergo dynamic changes caused by nonequilibrium relaxation in the lattice structure local to the photoexcitations (i.e., self-trapping). The α-phase of crystalline perylene is particularly well-suited for fundamental studies of exciton self-trapping mechanisms. It is generally agreed that a subpicosecond self-trapping process in α-perylene localizes photoexcited excitons onto pairs of closely spaced molecules (i.e., dimers), which then relax through excimer emission. Here, electronic relaxation dynamics in α-perylene single crystals are investigated using a variety of nonlinear optical spectroscopies in conjunction with a Frenkel exciton model. Linear absorption and photon echo spectroscopies suggest that excitons are delocalized over less than four unit cells (16 molecules) at 78 K prior to self-trapping. Stimulated Raman spectroscopies conducted on and off electronic resonance reveal significant vibronic coupling in a mode at 104 cm(-1), which corresponds to the displacement between perylene molecules comprising a dimer. Strong vibronic coupling in this mode suggests that motion along the interdimer axis is instrumental in driving the self-trapping process. The results are discussed in the context of our recent study of tetracene and rubrene single crystals in which similar experiments and models were employed.

Vibrational frequencies and tuning of the African mbira.

The acoustic spectrum of the mbira, a musical instrument from Africa that produces sound by the vibration of cantilevered metal rods, has been measured. It is found that the most prominent overtones present in the spectrum have frequencies that are approximately 5 and 14 times the lowest frequency. A finite-element model of the vibration of the key that takes into account the acoustic radiation efficiency of the various normal modes reveals that the far-field power spectrum is dominated by modes involving predominately transverse motion of the key. Modes involving longitudinal motion do not radiate efficiently, and therefore contribute little to the sound produced. The high frequencies of the dominant overtones relative to the fundamental make it unlikely that the tunings of the mbira that are used by expert musicians are determined by matching the fundamental frequencies of the upper keys with the overtones of the lower keys.

Synthesis and characterization of TiO2 nanotube/hydroquinone hybrid structure.

It is shown that 1,4-benzenediol (hydroquinone) and TiO2 nanotubes can form a hybrid structure that is stable in aqueous environment. The incorporation of hydroquinone restores the local structure of nanotubes to anatase-like as evidenced by Raman spectroscopy. Subtle overall structural changes take place upon annealing of the hybrid structure contributing to its stability. The hybrid system shows a broad optical absorption peak extending significantly beyond 700 nm with potential applications in photocatalysis and photoelectrochemistry.

Orientation dependence in near-field scattering from TiO(2) particles.

This scattering of light by small particles embedded in a continuous transparent medium is influenced not only by the bulk optical properties of the particles and the medium but also by the size, shape, and spatial arrangement of the particles-that is, by the microstructure. If the particles are close together, as in agglomerated coatings or stereolithographic suspensions, interactions between the radiation fields of adjacent particles can lead to variations in the magnitude and spatial arrangement of the scattered light in the near and the far field, which can affect the color and hiding power of a coating, the cure depth and homogeneity in stereolithography, and the threshold intensity for stimulated emission in random lasers. Our calculations of the near- and the far-field scattering distribution for 200-nm TiO(2) spheres in pairs of various orientations and in an ordered array of five particles show that, depending on the orientation of the particles with respect to the incident light, these interactions can either increase or decrease the scattering efficiency, the isotropy of the scattering, and the magnitude of the electric field strength within the matrix and the particles. In the mid-visible range, two particles in line increase the backscattering fraction by 28% and the scattering strength by 38% over that of a single particle, whereas if the particles are in the diagonal configuration the backscattering fraction and scattering strength are actually reduced by addition of the second particle. At shorter or longer wavelengths the backscattering fraction is reduced regardless of the location of the second particle, by as much as 60% when five particles are arranged in the zigzag configuration. These results are surprising in that it is generally assumed that multiple scattering enhances backscattering. Simple models of multiple scattering or scattering of two particles as a single, larger particle are inadequate to explain these results.